Mixture for the oxidation tinting of keratin fibers containing a laccase and tinting method using said mixture

ABSTRACT

The invention relates to a cosmetic mixture for the oxidation tinting of keratin fibers, especially human hair, comprising in a support material suitable for tinting keratin fibers (a) at least one laccase-type enzyme; (b) at least one particular conditioning agent for keratin fibers which is insoluble in aqueous media; and (c) at least one oxidation colorant. The invention also relates to the tinting methods using the above mixture.

The present invention relates to a composition for the oxidation dyeingof keratinous fibres comprising at least one enzyme of the laccase type,at least one oxidation dye and at least one particular keratinous fibreconditioning agent which is insoluble in aqueous media, as well as itsuses for dyeing keratinous fibres, in particular human hair.

It is known to dye keratinous fibres, and in particular human hair, withdyeing compositions containing oxidation dye precursors, in particularortho- and para-phenylenediamines, ortho- or para-aminophenols,heterocyclic bases generally called oxidation bases. The oxidation dyeprecursors, or oxidation bases, are colourless or weakly colouredcompounds which, combined with oxidizing products, can give rise to dyeand coloured compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases canbe varied by combining them with couplers or colour modifiers, thelatter being chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of molecules used in oxidation bases and couplers allows arich palette of colours to be obtained.

The so-called “permanent” colour obtained by means of these oxidationdyes should moreover satisfy a number of requirements. Thus, it shouldhave no drawbacks from the toxicological point of view, it should makeit possible to obtain shades of the desired intensity and it shouldexhibit good resistance towards external agents (light, adverse weatherconditions, washing, permanent waving, perspiration, rubbing).

The dyes should also make it possible to cover grey hair, and thusshould be the least selective possible, that is to say they should makeit possible to obtain the smallest possible differences in colour allalong the same keratinous fibre, which may indeed be differentlysensitized (i.e. damaged) between its tip and its root.

The oxidation dyeing of keratinous fibres is generally carried out in analkaline medium, in the presence of hydrogen peroxide. However, the useof alkaline media in the presence of hydrogen peroxide has thedisadvantage of causing substantial degradation of the fibres, as wellas decolouring of the keratinous fibres which is not always desirable.

The oxidation dyeing of keratinous fibres can also be carried out withthe aid of oxidizing systems different from hydrogen peroxide such asenzymatic systems. Thus, it has already been proposed in U.S. Pat. No.3,251,742, Patent Applications FR-A-2,112,549, FR-A-2,694,018,EP-A-0,504,005, WO95/07988, WO95/33836, WO95/33837, WO96/00290,WO97/19998 and WO97/19999 to dye keratinous fibres with compositionscomprising at least one oxidation dye in combination with enzymes of thelaccase type, the said compositions being brought into contact withatmospheric oxygen. These dyeing formulations, although used underconditions which do not cause degradation of the keratinous fibrescomparable to that caused by dyeings carried out in the presence ofhydrogen peroxide, lead to colours which are still inadequate both fromthe point of view of homogeneity of the colour distributed along thefibre (“unison”), from the point of view of chromaticity (luminosity)and of the dyeing power.

The aim of the present invention is to solve the problems mentionedabove.

The Applicant has surprisingly discovered novel compositions comprising,as oxidizing system, at least one enzyme of the laccase type and atleast one particular conditioning agent insoluble in aqueous media whichwill be defined in greater detail below, capable of constituting, in thepresence of at least one oxidation dye, ready-to-use dyeing formulationsgiving colours which are more homogeneous, more intense and morechromatic without causing significant degradation or decolouring of thekeratinous fibres, which exhibit low selectivity and good resistance tovarious attacks to which the hair may be subjected.

These discoveries form the basis of the present invention.

The first subject of the present invention is therefore a ready-to-usecomposition intended for the oxidation dyeing of keratinous fibres, inparticular human keratinous fibres and more particularly human hair,comprising, in a carrier appropriate for keratinous fibres:

(a) at least one enzyme of the laccase type;

(b) at least one conditioning agent insoluble in aqueous media, chosenfrom the group consisting of: poly-α-olefins, fluorinated oils,vegetable oils, natural waxes, fluorinated waxes, fluorinated gums,fatty acid esters chosen from ethyl and isopropyl palmitates,2-ethylhexyl palmitate, 2-octyldecyl palmitate, butyl, cetyl or2-octyldodecyl myristates, hexyl stearate, butyl stearate, dioctylmaleate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate,insoluble silicones, amide compounds comprising at least one fatty chainchosen from those of the following formula (1):

 in which:

R¹ denotes either a saturated or unsaturated, linear or branched, C₉-C₃₀hydrocarbon radical, it being possible for this radical to besubstituted with one or more hydroxyl groups optionally esterified witha saturated or unsaturated C₁₆-C₃₀ fatty acid; or a radicalR″—(NR—CO)_(n)—R′ in which n is equal to 0 or 1, R denotes hydrogen orhydroxyethyl, R′ and R″ are hydrocarbon radicals in which the sum of thecarbon atoms is between 9 and 30, R′ being a divalent radical,

R² denotes a hydrogen atom or a (glycosyl)_(n), (galactosyl)_(m) orsulphogalactosyl radical in which n is an integer varying from 1 to 4and m is an integer varying from 1 to 8;

R³ denotes a hydrogen atom or a saturated or unsaturated C₁₆-C₂₇hydrocarbon radical, it being possible for this radical to besubstituted with one or more C₁-C₁₄ alkyl radicals; R³ may also denote aC₁₅-C₂₆ α-hydroxyalkyl radical, the hydroxyl group being optionallyesterified with a C₁₆-C₃₀ α-hydroxy acid;

R⁴ denotes a hydrogen atom, a saturated or unsaturated C₁₆-C₂₇hydrocarbon radical or a radical —CH₂—CHOH—CH₂—O—R⁶ in which R denotes aC₁₀-C₂₆ hydrocarbon radical;

R⁵ denotes a hydrogen atom or a mono- or polyhydroxylated C₁-C₄hydrocarbon radical; it being possible for the said agents to be presentin the form of mixtures;

(c) at least one oxidation dye.

The laccase(s) used in the ready-to-use dye composition in accordancewith the invention may be chosen in particular from laccases of plantorigin, animal origin, fungal origin (yeasts, moulds, fungi) orbacterial origin, organisms which may be of mono- or pluricellularorigin. They can be obtained by biotechnology.

Among the laccases of plant origin which can be used according to theinvention, there may be mentioned the laccases produced by plants whichperform chlorophyll synthesis as indicated in Application FR-A-2,694,018such as those found in the extracts of Anacardiaceae such as for examplethe extracts of Magnifera indica, Schinus molle or Pleiogyniumtimoriense, in the extracts of Podocarpaceae, Rosmarinus off., Solanumtuberosum, Iris sp., Coffea sp., Daucus carrota, Vinca minor, Perseaamericana, Catharenthus roseus, Musa sp., Malus pumila, Gingko biloba,Monotropa hypopithys (Indian pipe), Aesculus sp., Acer pseudoplatanus,Prunus persica, Pistacia palaestina.

Among the laccases of fungal origin optionally obtained by biotechnologywhich can be used according to the invention, there may be mentioned thelaccase(s) derived from Polyporus versicolor, Rhizoctonia practicola andRhus vernicifera as indicated in Applications FR-A-2,112,549 andEP-A-504005, those described in Patent Application WO95/07988,WO95/33836, WO95/33837, WO96/00290, WO97/19998 and WO97/19999, whosecontent is an integral part of the present description, such as forexample those derived from Scytalidium, Polyporus pinsitus,Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, orvariants thereof. There may also be mentioned those derived fromTramates versicolor, Fomes fomentarius, Chaetomium thermophile,Neurospora crassa, Coriolus versicol, Botrytis cinerea, Rigidoporuslignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans,Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerellacingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum,Thelephora terrestris, Cladosporium cladosporiodes, Cerrena unicolor,Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus,Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune,Dichomitius squalens and variants thereof.

The laccases of fungal origin optionally obtained by biotechnology willbe preferably chosen.

The enzymatic activity of the laccases of the invention which havesyringaldazine among their substrates can be defined from the oxidationof syringaldazine under aerobic conditions. The lacu unit corresponds tothe quantity of enzyme catalysing the conversion of 1 mmol ofsyringaldazine per minute at pH, 5.5 at 30° C. The unit u corresponds tothe quantity of enzyme producing a delta absorbance at 530 nm of 0.001per minute using syringaldazine as substrate, at 30° C. and at pH 6.5.

The enzymatic activity of the laccases of the invention can also bedefined from the oxidation of para-phenylenediamine. The ulac unitcorresponds to the quantity of enzyme producing a delta absorbance at496.5 nm of 0.001 per minute using para-phenylenediamine as substrate(64 mM) at 30° C. and at pH 5. According to the invention, it ispreferable to determine the enzymatic activity in ulac units.

The quantities of laccase used in the compositions of the invention willvary according to the nature of the laccase chosen. Preferably, theywill vary from 0.5 to 2000 ulac, or from 1000 to 4×10⁷ u units, or from20 to 2×10⁶ ulac units per 100 g of composition.

The conditioning agents may be provided in liquid, semisolid or solidform, such as for example oils, waxes or gums.

According to the invention, among the conditioning agents, thepoly-α-olefins are in particular:

of the polybutene type, hydrogenated or otherwise, and preferably of thepolyisobutene type, hydrogenated or otherwise.

There are preferably used the oligomers of isobutylene having amolecular weight of less than 1000 and mixtures thereof withpolyisobutylenes having a molecular weight greater than 1000 andpreferably of between 1000 and 15,000.

By way of examples of poly-α-olefins which can be used in the context ofthe present invention, there may be mentioned more particularly theproducts sold under the name PERMETHYL 99 A, 101 A, 102 A, 104 A (n=16)and 106 A (n=38) by the company PRESPERSE Inc, or alternatively theproducts sold under the name ARLAMOL HD (n=3) by the company ICI (ndenoting the degree of polymerization),

of the polydecene type, hydrogenated or otherwise.

Such products are sold for example under the names ETHYLFLO by thecompany ETHYL CORP., and ARLAMOL PAO by the company ICI.

The fluorinated oils, fluorinated waxes and fluorinated gums are forexample the perfluoropoly-ethers described in Patent ApplicationEP-A-486135 and the fluorohydrocarbon compounds described in particularin Patent Application WO 93/11103. The teaching of these twoapplications is fully included in the present application by way ofreference.

The term fluorohydrocarbon compounds denotes compounds whose chemicalstructure comprises a carbon backbone in which some hydrogen atoms havebeen substituted with fluorine atoms.

The perfluoropolyethers are for example sold under the trade namesFOMBLIN by the company MONTEFLUOS and KRYTOX by the company DU PONT.

Among the fluorohydrocarbon compounds, there may also be mentioned thefluorinated fatty acid esters such as the product sold under the nameNOFABLE FO by the company NIPPON OIL.

According to the invention, the conditioning agents may be chosen fromvegetable oils such as jojoba oil, avocado oil or alternatively naturalwaxes such as carnauba wax or apple wax.

According to the invention, the conditioning agents may be chosen fromthe insoluble silicones normally used to improve the cosmetic propertiesof hair treated with hair formulations, namely in particular thosedescribed in Patent Applications EP-A-0181773 and EP-A-0473508.

It is of course possible to use mixtures of silicones.

Thus, according to the present invention, it is possible to use anysilicone known per se, whether it is an oil, a resin or alternatively asilicone gum. The silicones are organosilicon polymers or oligomershaving a branched or crosslinked, linear or cyclic structure, ofvariable molecular weight, which are obtained by polymerization and/orpolycondensation of suitably functionalized silanes, and essentiallyconsisting of a repetition of principal units in which the silicon atomsare linked to each other by oxygen atoms (siloxane bond), optionallysubstituted hydrocarbon radicals being directly linked via a carbon atomon the said silicon atoms. The most common hydrocarbon radicals are thealkyl, and in particular methyl, radicals, the fluoroalkyl radicals, thearyl, and in particular phenyl, radicals, and the alkenyl, and inparticular vinyl, radicals; other types of radicals which are capable ofbeing linked either directly, or via a hydrocarbon radical, to thesiloxane chain are in particular hydrogen, halogens and in particularchlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene(or polyether), and in particular polyoxyethylene and/orpolyoxypropylene, radicals, hydroxyl or hydroxyalkyl radicals,amphoteric or betaine groups, anionic groups such as carboxylates,thioglycolates, sulphosuccinates, thiosulphates, phosphates andsulphates, this list of course not being at all limiting (so-called“organomodified” silicones). In general, the silicones which can be usedin the context of the present invention are those which are inparticular described in “Encyclopedia of Chemical Technology,Kirk-Othmer, Third Edition, 1982, Volume 20, pp. 922 and the followingpages” and in “Chemistry and Technology of Silicones, Walter NOLL,Academic Press Inc, San Diego Calif., 1968”. It is also possible to uselinear block copolymers comprising, in their principal chain,polysiloxane segments, such as for example polysiloxane-polyoxyalkyleneor alternatively polysiloxane-polyurethane and/or polyurea blockcopolymers. The average molecular weight of the silicones which can beused according to the invention may vary between 100 and severalmillions, preferably between 1000 and 1,000,000. According to thepresent invention, it is of course possible to use either a singlesilicone, or use several different silicones.

By way of examples of silicones which can be used in the compositionsaccording to the invention, there may be mentioned in particularpolydialkyl-siloxanes, polyalkylarylsiloxanes,polydiaryldialkyl-siloxanes and more generally still all theorganopolysiloxanes described in the patent application published underthe number WO 93/05762 and whose teaching is, in this regard, fullyincluded in the present application by way of reference.

According to a particularly preferred embodiment of the presentinvention, the silicones used are chosen from diorganopolysiloxanes(oils, gums or resins), preferably polydialkylsiloxanes orpolyalkylarylsiloxanes, and still more preferably optionally modifiedpolydimethylsiloxanes.

The silicone gums are particularly preferred and in particular those ofpolydialkylsiloxanes or of polyalkylarylsiloxanes. They can be usedalone or as a mixture in a solvent chosen, for example, from volatilesilicones, polydimethylsiloxane or polyphenylmethyl-siloxane oils,isoparaffins, pentane, dodecane or mixtures thereof.

Among the amide compounds of formula (I), there are preferred theceramides and/or glycoceramides described by DOWNING in Arch. Dermatol,Vol. 123, 1381-1384, 1987, or those described in French PatentApplication FR-2673 79, whose teachings are included here by way ofreference.

The ceramides most particularly preferred according to the invention arethe compounds of formula (1) for which R¹ denotes a saturated orunsaturated alkyl derived from C₁₆-C₂₂ fatty acids; R² denotes ahydrogen atom; and R³ denotes a saturated linear C₁₅ radical.

Such compounds are for example:

N-linoleoyldihydrosphingosine,

N-oleoyldihydrosphingosine,

N-palmitoyldihydrosphingosine,

N-stearoyldihydrosphingosine,

N-behenoyldihydrosphingosine,

or the mixtures of these compounds.

It is also possible to use the compounds of formula (1) for which R¹denotes a saturated or unsaturated alkyl radical derived from fattyacids; R² denotes a galactosyl or sulphogalactosyl radical; and R³denotes a group —CH═CH—(CH₂)₁₂—CH₃.

By way of example, there may be mentioned the product consisting of amixture of glycoceramides, sold under the trade name GLYCOCER by thecompany WAITAKI INTERNATIONAL BIOSCIENCES.

It is also possible to use the compounds of formula (1) described inPatent Applications EP-A-0227994 and WO94/07844.

Such compounds are for example QUESTAMIDE H(bis(N-hydroxyethyl-N-cetyl)malonamide) sold by the company QUEST,N-(2-hydroxyethyl)-N-(3-Cetyloxy-2-hydroxypropyl)amide of cetylic acid.

It is possible to use the N-docasanoyl-N-methyl-D-glucamine described inPatent Application WO92/05764.

In the present invention, it is preferable to use, as conditioning agentinsoluble in aqueous media, natural waxes, vegetable oils, insolublesilicones and fatty amides as described above.

The conditioning agent(s) are present in the compositions in accordancewith the invention in proportions generally of between 0.001 and 10% byweight, preferably from 0.01 to 5% by weight, and still moreparticularly from 0.1 to 2% by weight relative to the total weight ofthe composition.

The nature of the oxidation dye(s) used in the ready-to-use dyeingcomposition is not critical. They are chosen from oxidation bases and/orcouplers.

The oxidation bases may be chosen in particular frompara-phenylenediamines, double bases, para-aminophenols,ortho-aminophenols and heterocyclic oxidation bases.

Among the para-phenylenediamines which can be used as oxidation base inthe dyeing composition in accordance with the invention, there may bementioned in particular the compounds of the following formula (I) andtheir addition salts with an acid:

in which:

R₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, amonohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy-(C₂-C4 alkyl) radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ alkyl radical substitutedwith a nitrogen-containing group, a phenyl radical or a 4′-aminophenylradical;

R₂ represents a hydrogen atom, a C₁-C₄ alkyl radical, amonohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy(C₂-C₄ alkyl) radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith a nitrogen-containing group;

R₃ represents a hydrogen atom, a halogen atom such as a chlorine,bromine, iodine or fluorine atom, a C₁-C₄ alkyl radical, amonohydroxy(C₁-C₄ alkyl) radical, a hydroxy(C₁-C₄ alkoxy) radical, anacetylamino(C₁-C4 alkoxy) radical, a mesylamino(C₁-C₄ alkoxy) radical ora carbamoylamino(C₁-C₄ alkoxy) radical,

R₄ represents a hydrogen or halogen atom or a C₁-C₄ alkyl radical.

Among the nitrogen-containing groups of formula (I) above, there may bementioned in particular the amino, mono(C₁-C₄)alkylamino,(C₁-C₄)dialkylamino, (C₁-C₄)trialkylamino, monohydroxy(C₁-C₄)alkylamino,imidazolinium and ammonium radicals.

Among the para-phenylenediamines of formula (I) above, there may bementioned more particularly para-phenylenediamine, para-tolylenediamine,2-Chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylene-diamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylene-diamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine, and their addition salts withan acid.

Among the para-phenylenediamines of formula (I) above, there are mostparticularly preferred para-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylene-diamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine,2-β-acetylaminoethyloxy-para-phenylenediamine, and their addition saltswith an acid.

According to the invention, “double bases” is understood to mean thecompounds containing at least two aromatic rings on which amino and/orhydroxyl groups are carried.

Among the double bases which can be used as oxidation bases in thedyeing compositions in accordance with the invention, there may bementioned in particular the compounds corresponding to the followingformula (II), and their addition salts with an acid:

in which:

Z₁ and Z₂, which are identical or different, represent a hydroxyl or—NH₂ radical which may be substituted with a C₁-C₄ alkyl radical or witha linking arm Y;

the linking arm Y represents a linear or branched alkylene chaincomprising from 1 to 14 carbon atoms, which may be interrupted by orwhich may end with one or more nitrogen-containing groups and/or one ormore heteroatoms such as oxygen, sulphur or nitrogen atoms, andoptionally substituted with one or more hydroxyl or C₁-C₆ alkoxyradicals;

R₅ and R₆ represent a hydrogen or halogen atom, a C₁-C₄ alkyl radical, amonohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy(C₂-C₄ alkyl) radical, anamino(C₁-C₄ alkyl) radical or a linking arm Y;

R₇, R₈, R₉, R₁₀, R₁₁ and R₁₂, which are identical or different,represent a hydrogen atom, a linking arm Y or a C₁-C₄ alkyl radical;

it being understood that the compounds of formula (II) contain only onelinking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, there may bementioned in particular the amino, mono(C₁-C₄)alkylamino, (C₁-C₄)dialkylamino, (C₁-C₄) trialkylamino, monohydroxy(C₁-C₄)alkylamino,imidazolinium and ammonium radicals.

Among the double bases of formulae (II) above, there may be mentionedmore particularlyN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis (4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylene-diamine,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition saltswith an acid.

Among these double bases of formula (II),N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,1,8-bis (2,5-diaminophenoxy)-3,5-dioxaoctane or one of their additionsalts with an acid are particularly preferred.

Among the para-aminophenols which can be used as oxidation bases in thedyeing compositions in accordance with the invention, there may bementioned in particular the compounds corresponding to the followingformula (III), and their addition salts with an acid:

in which:

R₁₃ represents a hydrogen or halogen atom, a C₁-C₄ alkyl, monohydroxy(C₁-C4 alkyl), (C₁-C₄) alkoxy(C₁-C₄)-alkyl, amino(C₁-C₄ alkyl) orhydroxy(C₁-C₄)alkylamino-(C₁-C₄ alkyl) radical,

R₁₄ represents a hydrogen or halogen atom, a C₁-C4 alkyl, monohydroxy(C₁-C4 alkyl), polyhydroxy (C₂-C₄ alkyl), amino(C₁-C₄ alkyl),cyano(C₁-C₄ alkyl) or (C₁-C4)alkoxy(C₁-C₄)alkyl radical,

it being understood that at least one of the radicals R₁₃ or R₁₄represents a hydrogen atom.

Among the para-aminophenols of formula (III) above, there may bementioned more particularly para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, andtheir addition salts with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in thedyeing compositions in accordance with the invention, there may bementioned more particularly 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and their additionsalts with an acid.

Among the heterocyclic bases which can be used as oxidation bases in thedyeing compositions in accordance with the invention, there may bementioned more particularly pyridine derivatives, pyrimidinederivatives, pyrazole derivatives, pyrazolopyrimidine derivatives, andtheir addition salts with an acid.

Among the pyridine derivatives, there may be mentioned more particularlythe compounds described for example in Patents GB 1,026,978 and GB1,153,196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine,and their addition salts with an acid.

Among the pyrimidine derivatives, there may be mentioned moreparticularly the compounds described for example in German Patent DE2,359,399 or Japanese Patents JP 88-169,571 and JP 91-333,495 or PatentApplication WO 96/15765, such as 2,4,5,6-tetra-aminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and theiraddition salts with an acid.

Among the pyrazole derivatives, there may be mentioned more particularlythe compounds described in Patents DE 3,843,892, DE 4,133,957 and Patentapplications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4′-chlorobenzyl)-pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methyl-pyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropyl-pyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylamino-pyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their additionsalts with an acid.

Among the pyrazolopyrimidine derivatives, there may be mentioned moreparticularly the pyrazolo[1,5-a]pyrimidines of the following formula(IV), their addition salts with an acid or with a base and theirtautomeric forms, when a tautomeric equilibrium exists:

in which:

R₁₅, R₁₆, R₁₇ and R₁₈, which are identical or different, denote ahydrogen atom, a C₁-C₄ alkyl radical, an aryl radical, a C₁-C₄hydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄ alkyl) radical, a C₁-C₄ aminoalkyl radical (it beingpossible for the amine to be protected with an acetyl, ureido orsulphonyl radical), a (C₁-C₄) alkylamino(C₁-C₄ alkyl) radical, adi-[(C₁-C₄)alkyl]amino(C₁-C₄ alkyl) radical (it being possible for thedialkyl radicals to form a carbon-containing ring or a 5- or 6-memberedheterocycle), a hydroxy(C₁-C₄)alkyl- ordi-[hydroxy(C₁-C₄)alkyl]-amino(C₁-C₄ alkyl) radical,

the X radicals, which are identical or different, denote a hydrogenatom, a C₁-C₄ alkyl radical, an aryl radical, a C₁-C₄ hydroxyalkylradical, a C₂-C₄ polyhydroxyalkyl radical, a C₁-C₄ aminoalkyl radical, a(C₁-C₄)alkylamino(C₁-C₄ alkyl) radical, a di-[(C₁-C₄)alkyl]amino(C₁-C₄alkyl) radical (it being possible for the dialkyls to form acarbon-containing ring or a 5- or 6-membered heterocycle), ahydroxy(C₁-C₄)alkyl or di-[hydroxy(C₁-C₄)alkyl]-amino(C₁-C₄ alkyl)radical, an amino radical, a (C₁-C₄)alkyl- or di-[(C₁-C₄)alkyl]-aminoradical; a halogen atom, a carboxylic acid group, a sulphonic acidgroup;

i equals 0, 1, 2 or 3;

p equals 0 or 1;

q equals 0 or 1;

n equals 0 or 1;

with the proviso that:

the sum p+q is different from 0;

when p+q is equal to 2, then n equals 0 and the groups NR₁₅R₁₆ andNR₁₇R₁₈ occupy positions (2,3); (5,6); (6,7); (3,5) or (3,7);

when p+q is equal to 1, then n equals 1 and the group NR₁₅R₁₆ (orNR₁₇R₁₈) and the OH group occupy positions (2,3); (5,6); (6,7); (3,5) or(3,7).

When the pyrazolo[1,5-a]pyrimidines of formula (IV) above are such thatthey comprise a hydroxyl group on one of the positions 2, 5 or 7 at theα position with respect to a nitrogen atom, a tautomeric equilibriumexists which is represented for example by the following scheme:

Among the pyrazolo[1,5-a]pyrimidines of formula (IV) above, there may bementioned in particular:

pyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

pyrazolo[1,5-a]pyrimidine-3,5-diamine;

2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;

3-aminopyrazolo[1,5-a]pyrimidin-7-ol;

3-aminopyrazolo[1,5-a]pyrimidin-5-ol;

2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;

2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;

2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxy-ethyl) amino]ethanol;

2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxy-ethyl)amino]ethanol;

5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

and their addition salts and their tautomeric forms, when a tautomericequilibrium exists.

The pyrazolo[1,5-a]pyrimidines of formula (IV) above may be prepared bycyclization from an aminopyrazole according to the syntheses describedin the following references:

EP 628559 BEIERSDORF-LILLY

R. Vishdu, H. Navedul, Indian J. Chem., 34b(6), 514, 1995.

N. S. Ibrahim, K. U. Sadek, F. A. Abdel-Al, Arch. Pharm., 320, 240,1987.

R. H. Springer, M. B. Scholten, D. E. O'Brien, T. Novinson, J. P.Miller, R. K. Robins, J. Med. Chem., 25, 235, 1982.

T. Novinson, R. K. Robins, T. R. Matthews, J. Med. Chem., 20, 296, 1977.

U.S. Pat. No. 3,907,799 ICN PHARMACEUTICALS

The pyrazolo[1,5-a]pyrimidines of formula (IV) above can also beprepared by cyclization from ydrazine according to the synthesesdescribed in the following references:

A. McKillop and R. J. Kobilecki, Heterocycles, 6(9), 1355, 1977.

E. Alcade, J. De Mendoza, J. M. Marcia-Marquina, C. Almera, J. Elguero,J. Heterocyclic Chem., 11(3), 423, 1974.

K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan,47(2), 476, 1974.

The oxidation base(s) preferably represent from 0.0005 to 12% by weightapproximately of the total weight of the dyeing composition inaccordance with the invention, and still more preferably from 0.005 to6% by weight approximately of this weight.

The coupler(s) which can be used in the ready-to-use dyeing compositionin accordance with the invention are those conventionally used inoxidation dyeing compositions, that is to say meta-phenylene-diamines,meta-aminophenols, meta-diphenols, heterocyclic couplers, and theiraddition salts with an acid.

These couplers may be chosen in particular from 2-methyl-5-aminophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxy-benzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethyl-pyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-C]-1,2,4-triazole,6-methylpyrazolo[1,5-a]benzimidazole, and their addition salts with anacid.

These couplers preferably represent from 0.0001 to 10% by weightapproximately of the total weight of the ready-to-use dyeingcomposition, and still more preferably from 0.005 to 5% by weightapproximately of this weight.

In general, the addition salts with an acid of the oxidation dyes whichcan be used in the context of the dyeing compositions of the invention(oxidation bases and couplers) are in particular chosen fromhydrochlorides, hydrobromides, sulphates and tartrates, lactates andacetates.

The dyeing composition of the invention may also contain, in addition tothe oxidation dyes defined above, direct dyes in order to increase theshimmer of the shades. These direct dyes may in particular then bechosen from nitro, azo or anthraquinone dyes.

The ready-to-use dyeing composition in accordance with the invention mayalso contain various adjuvants conventionally used in hair dyeingcompositions, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, polymers, thickeners,antioxidants, enzymes different from the laccases used in accordancewith the invention, such as for example peroxidases or oxido-reductasescontaining 2 electrons, penetrating agents, sequestering agents,perfumes, buffers, dispersing agents, film-forming agents, screeningagents, vitamins, preservatives or opacifying agents.

Of course, persons skilled in the art will be careful to choose this orthese optional additional compounds such that the advantageousproperties intrinsically attached to the ready-to-use dyeing compositionin accordance with the invention are not, or substantially not, impairedby the addition(s) envisaged.

The ready-to-use dyeing composition in accordance with the invention canbe provided in various forms, such as in the form of liquids, creams,gels, optionally pressurized, or in any other form appropriate fordyeing keratinous fibres, in particular human hair. In this case, theoxidation dye(s) and the laccase(s) are present in the same ready-to-usecomposition, and consequently the said composition should be free ofgaseous oxygen, so as to avoid any premature oxidation of the oxidationdye(s).

The subject of the invention is also a method of dyeing keratinousfibres, and in particular human keratinous fibres such as hair, usingthe ready-to-use dyeing composition as defined above.

According to this method, at least one ready-to-use dyeing compositionas defined above is applied to the fibres for a sufficient time todevelop the desired colour, after which they are rinsed, optionallywashed with shampoo, rinsed again and dried.

The time necessary for the development of the colour on the keratinousfibres is generally between 3 and 60 minutes and still more precisely 5and 40 minutes.

According to one particular embodiment of the invention, the methodcomprises a preliminary step consisting in storing in a separate form,on the one hand, a composition (A) comprising, in a medium appropriatefor dyeing, at least one oxidation dye as defined above and, on theother hand, a composition (B) containing, in a medium appropriate fordyeing, at least one enzyme of the laccase type and at least oneconditioning agent insoluble in aqueous media as defined above, and thenin mixing them at the time of use before applying this mixture to thekeratinous fibres.

According to a particular embodiment of the invention, the insolubleconditioning agent may be incorporated into the composition (A).

Another subject of the invention is a multi-compartment device or dyeing(kit) or any other multi-compartment packaging system in which a firstcomparment contains the composition (A) as defined above and a secondcompartment contains a composition (B) as defined above. These devicesmay be equipped with a means which makes it possible to deliver thedesired mixture to the hair, such as the devices described in PatentFR-2,586,913 in the name of the applicant.

The medium appropriate for keratinous fibres (or carrier) of theready-to-use dyeing compositions for keratinous fibres in accordancewith the invention generally consists of water or of a mixture of waterand of at least one organic solvent in order to solubilize the compoundswhich might not be sufficiently soluble in water. As organic solvent,there may be mentioned for example C₁-C₄ alkanols such as ethanol andisopropanol as well as aromatic alcohols such as benzyl alcohol, similarproducts and mixtures thereof.

The solvents may be present in proportions preferably of between 1 and40% by weight approximately relative to the total weight of the dyeingcomposition, and still more preferably between 5 and 30% by weightapproximately.

The pH of the ready-to-use dyeing compositions for keratinous fibres inaccordance with the invention is chosen such that the enzymatic activityof the laccase is not impaired. It generally varies from 4 to 11approximately, and more preferably from 6 to 9 approximately.

Concrete examples illustrating the invention will now be given.

In the text which follows and in the preceding text, unless otherwisestated, the percentages are expressed by weight. The following examplesillustrate the invention with no limitation being implied.

EXAMPLE Dyeing Composition

The following ready-to-use dyeing composition was prepared (contents ingrams):

Laccase obtained from Rhus vernicifera 1.8 g containing 180 units/mgmarketed by the company SIGMA

(C₈-C₁₀)Alkyl polyglucoside in aqueous 16.5 g solution containing 60% ofactive substance (AS) sold under the name ORAMIX CG110 by the companySEPPIC

Paraphenylenediamine 0.254 g

2,4-Diaminophenoxyethanol dihydrochloride 0.260 g.

Dimethicone sold under the name MIRASIL 0.5 g DM 500,000 by the companyRHONE POULENC

Ethanol 20.0 g

pH agent qs pH 6.5

Demineralized water qs 100 g

This ready-to-use dyeing composition is applied to locks of natural greyhair which is 90% white for 40 minutes at 30° C. The hair is thenrinsed, washed with a standard shampoo and then dried.

Locks of hair with bluish grey colour are obtained.

In this example, 1.8 g of laccase obtained from Rhus verniciferacontaining 180 units/mg can be replaced with 1 g of laccase obtainedfrom Pyricularia Orizae containing 100 units/mg sold by the companyI.C.N.

What is claimed is:
 1. A composition for the oxidation dyeing ofkeratinous fibers, comprising: (a) at least one enzyme of the laccasetype; (b) at least one conditioning agent insoluble in aqueous media,chosen from poly-α-olefins, fluorinated oils, vegetable oils, naturalwaxes, fluorinated waxes, fluorinated gums, fatty acid esters chosenfrom ethyl and isopropyl palmitates, 2-ethylhexyl palmitate,2-octyidecyl palmitate, butyl, cetyl and 2-octyidodecyl myristates,hexyl stearate, butyl stearate, dioctyl maleate, hexyl laurate,2-hexyldecyl laurate and isononyl isononanate, silicones, and amidecompounds comprising at least one fatty chain chosen from those of theformula (1):

 in which: R¹ is chosen from saturated and unsaturated, linear andbranched, C₉-C₃₀ hydrocarbon groups, it being possible for these groupsto be substituted with at least one substituent chosen from hydroxylgroups optionally esterified with an acid chosen from saturated andunsaturated C₁₆-C₃₀ fatty acids, and R″—(NR—CO)_(n)—R′— groups in whichn is equal to 0 or 1, R is chosen from a hydrogen atom and hydroxyethylgroups, R′ and R″ are identical or different and are each chosen fromhydrocarbon groups, optionally substituted, in which the sum of thecarbon atoms varies from 9 to 30, R′ being a divalent group; R² ischosen from a hydrogen atom, (glycosyl)_(n) groups, (galactosyl)_(m)groups and sulphogalactosyl groups in which n is an integer varying from1 to 4 and m is an integer varying from 1 to 8; R³ is chosen from ahydrogen atom, saturated and unsaturated C₁₅-C₂₇ hydrocarbon groups, itbeing possible for these groups to be substituted with at least oneC₁-C₁₄ alkyl group; R³ may also be chosen from C₁₅-C₂₆ α-hydroxyalkylgroups, wherein the hydroxyl group of said α-hydroxyalkyl group isoptionally esterified with an acid chosen from C₁₆-C₃₀ α-hydroxy acids;R⁴ is chosen from a hydrogen atom, saturated and unsaturated C₁₆-C₂₇hydrocarbon groups, optionally substituted, and —CH₂—CHOH—CH₂—O—R⁶groups in which R⁶ is chosen from C₁₀-C₂₆ hydrocarbon groups, optionallysubstituted; R⁵ is chosen from a hydrogen atom and mono- andpolyhydroxylated C₁-C₄ hydrocarbon groups; and (c) at least oneoxidation dye.
 2. A composition according to claim 1, wherein saidkeratinous fibers are human keratinous fibers.
 3. A compositionaccording to claim 2, wherein said human keratinous fibers are hair. 4.A composition according to claim 1, wherein said at least one enzyme ofthe laccase type is chosen from laccases of plant origin, animal origin,fungal origin, and bacterial origin, and laccases obtained bybiotechnology.
 5. A composition according to claim 1, wherein said atleast one enzyme of the laccase type is chosen from those produced byplants performing chlorophyll synthesis.
 6. A composition according toclaim 1, wherein said at least one enzyme of the laccase type is chosenfrom those extracted from plants chosen from Anacardiaceae,Podocarpaceae, Rosmarinus off., Solanum tuberosum, Iris sp., Coffea sp.,Daucus carrota, Vinca minor, Persea americana, Catharenthus roseus, Musasp., Malus pumila, Gingko biloba, Monotropa hypopithys, Aesculus sp.,Acer pseudoplatanus, Prunus persica, and Pistacia palaestina.
 7. Acomposition according to claim 1, wherein said at least one enzyme ofthe laccase type is chosen from those derived from fungi chosen fromPyricularia orizae, Polyporus versicolor, Rhizoctonia praticola, Rhusvernicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila,Rhizoctonia solani, Tramates versicolor, Fomes fomentarius, Chaetomiumthermophile, Neurospora crassa, Coriolus versicol, Botrytis cinerea,Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillusnidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum,Glomerella cingulata, Lactarius piperatus, Russula delica,Heterobasidion annosum, Thelephora terrestris, Cladosporiumcladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsissubvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolussphinctrinus, Schizophyllum commune, Dichomitius squalens and variantsof all of said fungi.
 8. A composition according to claim 1, whereinsaid at least one enzyme of the laccase type is in a quantity rangingfrom 0.5 to 2000 lacu units per 100 g of said composition.
 9. Acomposition according to claim 1, wherein said at least one enzyme ofthe laccase type is in a quantity ranging from 1000 to 4×10⁷ u units per100 g of said composition.
 10. A composition according to claim 1,wherein said at least one enzyme of the laccase type is in a quantityranging from 20 to 2×10⁶ lacu units per 100 g of said composition.
 11. Acomposition according to claim 1, wherein said at least one conditioningagent is in liquid, semisolid or solid form.
 12. A composition accordingto claim 11, wherein said at least one conditioning agent is in the formof an oil, wax or gum.
 13. A composition according to claim 1, whereinsaid at least one conditioning agent is chosen from vegetable oils,natural waxes, silicones and the amide compounds of formula (1).
 14. Acomposition according to claim 1, wherein said poly-α-olefins are chosenfrom polybutene type groups, optionally hydrogenated, and polydecenetype groups, optionally hydrogenated.
 15. A composition according toclaim 14, wherein said polybutene type groups are polyisobutene typegroups, optionally hydrogenated.
 16. A composition according to claim 1,wherein said silicones are chosen from polydialkylsiloxanes,polyalkylarylsiloxanes, and polydiaryldialkylsiloxanes, optionallysubstituted.
 17. A composition according to claim 1, wherein saidsilicones are chosen from polydialkylsiloxanes andpolyalkylarylsiloxanes, optionally substituted.
 18. A compositionaccording to claim 1, wherein said silicones are polydimethylsiloxanes,optionally substituted.
 19. A composition according to claim 1, whereinsaid silicones are chosen from polydialkylsiloxane gumsandpolyalkylarylsiloxane gums.
 20. A composition according to claim 1,wherein in formula (1) of the amide compounds, R¹ is chosen fromsaturated and unsaturated alkyl groups derived from C₁₆-C₂₂ fatty acids;R² is a hydrogen atom; and R³ is a saturated linear C₁₅ group.
 21. Acomposition according to claim 1, wherein said amide compounds arechosen from: N-linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine,N-palmitoydihydrosphingosine, N-stearoyldihydrosphingosine,andN-behenoyidihydrosphingosine.
 22. A composition according to claim 1,wherein in formula (1) of said amide compounds, R¹ is chosen fromsaturated and unsaturated alkyl groups derived from fatty acids; R² ischosen from galactosyl groups and sulphogalactosyl groups; and R³ is thegroup —CH═CH—(CH₂)₁₂—CH₃.
 23. A composition according to claim 1,wherein said at least one conditioning agent is present in aconcentration ranging from 0.001% to 10% by weight relative to the totalweight of the composition.
 24. A composition according to claim 23,wherein said at least one conditioning agent is present in aconcentration ranging from 0.01% to 5% by weight relative to the totalweight of the composition.
 25. A composition according to claim 24,wherein said at least one conditioning agent is present in aconcentration ranging from 0.1% to 2% by weight relative to the totalweight of the composition.
 26. A composition according to claim 1,wherein said at least one oxidation dye is at least one oxidation basechosen from ortho- and para-phenylenediamines,bisphenylalkylenediamines, ortho- and para-aminophenols, heterocyclicbases, and the acid addition salts of all of said at least one oxidationbases.
 27. A composition according to claim 26, wherein said at leastone oxidation base is present in a concentration ranging from 0.0005% to12% by weight relative to the total weight of the composition.
 28. Acomposition according to claim 1, wherein said at least one oxidationdye is at least one coupler chosen from meta-phenylenediamines,meta-aminophenols, meta-diphenols, heterocyclic couplers, and the acidaddition salts of all of said at least one couplers.
 29. A compositionaccording to claim 28, wherein said at least one coupler is present in aconcentration ranging from 0.0001% to 10% by weight relative to thetotal weight of the composition.
 30. A composition according to claim26, wherein said acid addition salts are chosen from hydrochlorides,hydrobromides, sulphates, tartrates, lactates and acetates.
 31. Acomposition according to claim 28, wherein said acid addition salts arechosen from hydrochlorides, hydrobromides, sulphates, tartrates,lactates and acetates.
 32. A composition according to claim 1, furthercomprising at least one direct dye.
 33. A composition according to claim1, further comprising at least one carrier appropriate for keratinousfibers.
 34. A composition according to claim 33, wherein said at leastone carrier comprises a substance chosen from water and at least oneorganic solvent.
 35. A composition according to claim 34, wherein saidat least one organic solvent is present in a concentration ranging from1% to 40% by weight relative to the total weight of the composition. 36.A composition according to claim 35, wherein said at least one organicsolvent is present in a concentration ranging from 5% to 30% by weightrelative to the total weight of the composition.
 37. A compositionaccording to claim 1, wherein the pH varies from about 4 to about 11.38. A composition according to claim 37, wherein the pH varies fromabout 6 to about
 9. 39. A composition according to claim 1, furthercomprising at least one suitable cosmetic adjuvant chosen fromsurfactants, polymers, thickening agents, anitoxids, enzymes differentfrom said at least one enzyme of the laccase type as defined in claim 1,penetrating agents, sequestering agents, perfumes, buffers, dispersingagents, film-forming agents, screening agents, vitamins, preservativesand opacifying agents.
 40. A method of dyeing keratinous fibers,comprising applying to said keratinous fibers for a sufficient time todevelop a desired color at least one dyeing composition comprising: (a)at least one enzyme of the laccase type; (b) at least one conditioningagent insoluble in aqueous media, chosen from poly-α-olefins,fluorinated oils, vegetable oils, natural waxes, fluorinated waxes,fluorinated gums, fatty acid esters chosen from ethyl and isopropylpalmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, butyl, cetyland 2-octyldodecyl myristates, hexyl stearate, butyl stearate, dioctylmaleate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate,silicones, and amide compounds comprising at least one fatty chainchosen from those of the formula (1):

 in which: R¹ is chosen from saturated and unsaturated, linear andbranched, C₉-C₃₀ hydrocarbon groups, it being possible for these groupsto be substituted with at least one substituent chosen from hydroxylgroups optionally esterified with an acid chosen from saturated andunsaturated C₁₆-C₃₀ fatty acids, and R″—(NR—CO)_(n)—R′— groups in whichn is equal to 0 or 1, R is chosen from a hydrogen atom and hydroxyethylgroups, R′ and R″ are identical or different and are each chosen fromhydrocarbon groups, optionally substituted, in which the sum of thecarbon atoms varies from 9 to 30, R′ being a divalent group; R² ischosen from a hydrogen atom, (glycosyl)_(n) groups, (galactosyl)_(m)groups and sulphogalactosyl groups in which n is an integer varying from1 to 4 and m is an integer varying from 1 to 8; R³ is chosen from ahydrogen atom, saturated and unsaturated C₁₅-C₂₇ hydrocarbon groups, itbeing possible for these groups to be substituted with at least oneC₁-C₁₄ alkyl group; R³ may also be chosen from C₁₅-C₂₆ α-hydroxyalkylgroups, wherein the hydroxyl group of said α-hydroxyalkyl group isoptionally esterified with an acid chosen from C₁₆-C₃₀ α-hydroxy acids;R⁴ is chosen from a hydrogen atom, saturated and unsaturated C₁₆-C₂₇hydrocarbon groups, optionally substituted, and —CH₂—CHOH—CH₂—O—R⁶groups in which R⁶ is chosen from C₁₀-C₂₆ hydrocarbon groups, optionallysubstituted; R⁵ is chosen from a hydrogen atom and mono- andpolyhydroxylated C₁-C₄ hydrocarbon groups; and (c) at least oneoxidation dye.
 41. A method of dyeing keratinous fibers according toclaim 40, wherein said keratinous fibers are human keratinous fibers.42. A method of dyeing keratinous fibers according to claim 41, whereinsaid human keratinous fibers are hair.
 43. A method of dyeing keratinousfibers, comprising the steps of (a) storing a first composition, (b)storing a second composition separately from said first composition, (c)mixing the first composition with the second composition to form amixture, and (d) applying said mixture to said keratinous fibers for atime sufficient to achieve a desired coloration, wherein said firstcomposition comprises, in a medium appropriate for dyeing, at least oneoxidation dye, wherein said second composition comprises, in a mediumappropriate for keratinous fibers, at least one enzyme of the laccasetype, and further wherein at least one of said first composition andsaid second composition comprises at least one conditioning agentinsoluble in aqueous media, chosen from poly-α-olefins, fluorinatedoils, vegetable oils, natural waxes, fluorinated waxes, fluorinatedgums, fatty acid esters chosen from ethyl and isopropyl palmitates,2-ethylhexyl palmitate, 2-octyidecyl palmitate, butyl, cetyl and2-octyldodecyl myristates, hexyl stearate, butyl stearate, dioctylmaleate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate,silicones, and amide compounds comprising at least one fatty chainchosen from those of the formula (1):

 in which: R¹ is chosen from saturated and unsaturated, linear andbranched, C₉-C₃₀ hydrocarbon groups, it being possible for these groupsto be substituted with at least one substituent chosen from hydroxylgroups optionally esterified with an acid chosen from saturated andunsaturated C₁₆-C₃₀ fatty acids, and R″—(NR—CO)_(n)—R′— groups in whichn is equal to 0 or 1, R is chosen from a hydrogen atom and hydroxyethylgroups, R′ and R″ are identical or different and are each chosen fromhydrocarbon groups, optionally substituted, in which the sum of thecarbon atoms varies from 9 to 30, R′ being a divalent group; R² ischosen from a hydrogen atom, (glycosyl)_(n) groups, (galactosyl)_(m)groups and sulphogalactosyl groups in which n is an integer varying from1 to 4 and m is an integer varying from 1 to 8; R³ is chosen from ahydrogen atom, saturated and unsaturated C₁₅-C₂₇ hydrocarbon groups, itbeing possible for these groups to be substituted with at least oneC₁-C₁₄ alkyl group; R³ may also be chosen from C₁₅-C₂₆ α-hydroxyalkylgroups, wherein the hydroxyl group of said α-hydroxyalkyl group isoptionally esterified with an acid chosen from C₁₆-C₃₀ α-hydroxy acids;R⁴ is chosen from a hydrogen atom, saturated and unsaturated C₁₆-C₂₇hydrocarbon groups, optionally substituted, and —CH₂—CHOH—CH₂—O—R⁶groups in which R⁶ is chosen from C₁₀-C₂₆ hydrocarbon groups, optionallysubstituted; R⁵ is chosen from a hydrogen atom and mono- andpolyhydroxylated C₁-C₄ hydrocarbon groups.
 44. A multicompartment deviceor a dyeing kit, comprising a first compartment containing a composition(A) comprising, in a medium appropriate for dyeing, at least oneoxidation dye and a second compartment containing a composition (B)comprising, in a medium appropriate for keratinous fibers, at least oneenzyme of the laccase type, wherein at least one of said composition (A)and composition (B) comprises at least one conditioning agent insolublein aqueous media, chosen from poly-α-olefins, fluorinated oils,vegetable oils, natural waxes, fluorinated waxes, fluorinated gums,fatty acid esters chosen from ethyl and isopropyl palmitates,2-ethylhexyl palmitate, 2-octyldecyl palmitate, butyl, cetyl and2-octyldodecyl myristates, hexyl stearate, butyl stearate, dioctylmaleate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate,silicones, and amide compounds comprising at least one fatty chainchosen from those of the formula (1):

in which: R¹ is chosen from saturated and unsaturated, linear andbranched, C₉-C₃₀ hydrocarbon groups, it being possible for these groupsto be substituted with at least one substituent chosen from hydroxylgroups optionally esterified with an acid chosen from saturated andunsaturated C₁₆-C₃₀ fatty acids, and R″—(NR—CO)_(n)—R′— groups in whichn is equal to 0 or 1, R is chosen from a hydrogen atom and hydroxyethylgroups, R′ and R″ are identical or different and are each chosen fromhydrocarbon groups, optionally substituted, in which the sum of thecarbon atoms varies from 9 to 30, R′ being a divalent group; R² ischosen from a hydrogen atom, (glycosyl)_(n) groups, (galactosyl)_(m)groups and sulphogalactosyl groups in which n is an integer varying from1 to 4 and m is an integer varying from 1 to 8; R³ is chosen from ahydrogen atom, saturated and unsaturated C₁₅-C₂₇ hydrocarbon groups, itbeing possible for these groups to be substituted with at least oneC₁-C₁₄ alkyl group; R³ may also be chosen from C₁₅-C₂₆ α-hydroxyalkylgroups, wherein the hydroxyl group of said α-hydroxyalkyl group isoptionally esterified with an acid chosen from C₁₆-C₃₀ α-hydroxy acids;R⁴ is chosen from a hydrogen atom, saturated and unsaturated C₁₆-C₂₇hydrocarbon groups, optionally substituted, and —CH₂—CHOH—CH₂—O—R⁶groups in which R⁶ is chosen from C₁₀-C₂₆ hydrocarbon groups, optionallysubstituted; R⁵ is chosen from a hydrogen atom and mono andpolyhydroxylated C₁-C₄ hydrocarbon groups.